Organoarsine Metal-Organic Framework with cis-Diarsine Pockets for the Installation of Uniquely Confined Metal Complexes

Article abstract of DOI:10.1021/jacs.8b05644

ACM-1 is the first example of an organoarsine metal-organic framework (MOF), prepared using a new pyridyl-functionalized triarylarsine ligand coordinated to Ni(II) nodes. ACM-1 has micropores that are decorated with cis-diarsine coordination pockets. Postsynthetic metalation of ACM-1 with AuCl under facile conditions studied by single-crystal X-ray diffraction reveals the installation of dimeric Au₂Cl₂ complexes via the formation of As-Au bonds. The Au(I) dimers display exceptionally short aurophilic bonds (2.76 ?) induced by the rigidity of the MOF, which acts as a unique solid-state ligand.

Full text of DOI:10.1021/jacs.8b05644

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Communication
An Organoarsine MOF with cis-Diarsine Pockets for
the Installation of Uniquely Confined Metal Complexes
R. Eric Sikma, Pranaw Kunal, Samuel G. Dunning, Joseph E.
Reynolds, Ji Sun Lee, Jong-San Chang, and Simon M. Humphrey
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b05644 • Publication Date (Web): 20 Jul 2018
Downloaded from http://pubs.acs.org on July 20, 2018
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An Organoarsine MOF with cis-Diarsine Pockets for the Installation
of Uniquely Confined Metal Complexes
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R. Eric Sikma,a Pranaw Kunal,a Samuel G. Dunning,a Joseph E. Reynolds IIIa Ji Sun Lee,b JongꢀSan
Changb and Simon M. Humphrey*,a
a Department of Chemistry, The University of Texas at Austin, 105 E. 24th St. A5300, Austin, TX 78712ꢀ1224.
b Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusung, Daejeon,
305ꢀ600, Korea.
Supporting Information Placeholder
phosphines,5 amines6). However, it is difficult to control
ABSTRACT: ACMꢀ1 is the first example of an orꢀ
MOF assembly on a level that permits the formation of
structurallyꢀprecise chelate sites. This problem can be
overcome by postꢀsynthetic installation of chelating
moieties via organic coupling reactions, as demonstrated
by Cohen, Yaghi, Lin and others.7 Alternatively, preꢀ
formed molecular chelate complexes can be used to preꢀ
pare MOFs, as demonstrated recently by our group and
Wade et al. to obtain bis(phosphine)ꢀ8 and PCPꢀpincerꢀ
based MOFs.9
ganoarsine MOF, prepared using a new pyridylꢀ
functionalized triarylarsine ligand coordinated to Ni(II)
nodes. ACMꢀ1 has micropores that are decorated with
cisꢀdiarsine coordination pockets. Postꢀsynthetic metalꢀ
lation of ACMꢀ1 with AuCl under facile conditions studꢀ
ied by singleꢀcrystal Xꢀray diffraction reveals the instalꢀ
lation of dimeric Au2Cl2 complexes via the formation of
As‒Au bonds. The Au(I) dimers display exceptionally
short aurophilic bonds (2.76 Å) induced by the rigidity
of the MOF, which acts as a unique solidꢀstate ligand.
SSLꢀMOFs present a unique and exciting opportunity
to generate coordination complexes in ‘nonꢀequilibrium’
states, by exploiting the inherent rigidity of a MOF to fix
donor atoms in specific positions, thus imposing geoꢀ
metric strain on coordinated metal centers. The imposiꢀ
tion of nonꢀequilibrium metalꢀligand bond distances or
angles is wellꢀstudied in molecular catalysis as a means
to tune the electron density at a metal site, , e.g., through
ligand steric bulk effects.10
Metalꢀorganic frameworks (MOFs) hold unique potenꢀ
tial as structurally wellꢀdefined ‘solidꢀstate ligands’
(SSLs) to support the confinement of unusual lowꢀvalent
coordination complexes within their micropores. Hetꢀ
erogenized singleꢀsite complexes can effect various
small molecule transformations,1 enhance gas sorption
via strong adsorbate interactions at the open metal sites,2
and may be operated in liquidꢀ and gasꢀphase environꢀ
ments that molecular analogues cannot tolerate.3
As an example of this hypothesis, we recently reported
a triphenylphosphineꢀbased SSLꢀMOF called PCMꢀ101,
which is decorated with Lewis basic phosphineꢀP sites
arranged in transꢀorientations inside the pores.11 Postꢀ
synthetic installation of Cu2Br2 dimers tracked by sinꢀ
gleꢀcrystal Xꢀray diffraction revealed the imposition of
compressive strain, resulting in unusually short Cu···Cu
distances because the P···P separation in PCMꢀ101 was
~5% shorter than the average distance observed in moꢀ
lecular analogues.11
MOFs that permit postꢀsynthetic coordination of lowꢀ
valent transition metal complexes are comparatively
rare, especially examplesthat can form stable chelates.
Chelating ligands are of great importance in organomeꢀ
tallic chemistry and catalysis, but preparing SSLꢀMOFs
with similar moieties presents a synthetic challenge.4–9
Such MOFs can be prepared directly using Lewis base
ligands that are ubiquitous in molecular catalysts (e.g.,
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Journal of the American Chemical Society
Based on this compelling initial result, we began to
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search for routes to prepare other MOFs with similar
coordination pockets. Simultaneously, we decided to
investigate the preparation of MOFs based on triꢀ
arylarsines (AsAr3), referred to as Arsine Coordination
Materials (ACMs). To the best of our knowledge, there
are no prior reports of triarylarsineꢀbased MOFs, even
though arsines are commonplace in organometallic
chemistry.12 Organoarsines are structurally and chemiꢀ
cally similar to organophosphines but are less basic beꢀ
cause the Asꢀ4sp3 lone pair is more diffuse. For this
reason, arylarsines are commonly used as phosphine
surrogates to modulate catalytic reactivity.13 However,
leaching is a major consideration industrially, due to the
toxicity of As(III) and As(V) species.14 We propose that
the construction of Asꢀbased MOFs can directly mitigate
As toxicity issues because MOFs have zero volatility
and are more stable than molecular ligands. ACMꢀSSLs
could provide unique catalytic platforms, and may also
find utility in the sequestration of toxic heavy metals
(e.g., Cd(II)) from aqueous media.15
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Figure 1. (A) The extended asymmetric unit of ACMꢀ1 showing
the basic network connectivity; BPD ligands are drawn in cyan.
(B) Alternative view of an 8ꢀconnected [Ni2(ꢁ2ꢀOH)]3+ node. (C)
The distorted pyramidal environment of the As(III) donor site,
and bond angles (°).
of [Ni2(ꢁ2ꢀOH)]3+ dimers that are syn,synꢀbridged by
equivalent carboxylate groups of the dianionic BPD pilꢀ
laring ligand and a ꢁ2ꢀOH (Figure 1B). The octahedral
coordination environment of Ni1 is completed by facꢀ
oriented Nꢀdonors; each [Ni2(ꢁ2ꢀOH)]3+ unit is a 8ꢀ
connected node with bicapped trigonal prismatic geomeꢀ
try. The C–As–C bond angles range between 98.6–
101.0°, confirming that each As has an available lone
pair (Figure 1C).
With this in mind, we synthesized the AsAr3 ligand,
tris(4ꢀ(pyridinꢀ4ꢀyl)phenyl)arsine (TPPA; Scheme 1).
TPPA was prepared in gram quantities by lithiumꢀ
halogen exchange and Suzuki coupling (Scheme
1(i),(ii)). As a MOF building block, TPPA is a 3ꢀD, 3ꢀ
connected trigonal pyramidal linker with extended pheꢀ
nylpyridine arms and ancillary pyridylꢀN donors. The
substantially different coordination affinities of ‘hard’ N
and ‘soft’ As donors in TPPA facilitates the direct forꢀ
mation of MOFs with vacant As: sites using 3dꢀ
transition metals, via selective binding to Nꢀatoms.
ACMꢀ1 has a 3ꢀD micropore structure with three types
of pore windows. (Figures 2 & S4). The 3ꢀfold symꢀ
metry of the TPPA ligands engenders triangular openꢀ
ings with a maximum accessible edge length of 13.4 Å
lying parallel to the crystallographic aꢀaxis (Figure 2A).
The largest, rhombusꢀshaped openings have accessible
cornerꢀtoꢀcorner dimensions of 14.4 × 15.7 Å (Figure
2B). Smaller hexagonal pores of accessible diameter =
14. 3 Å lie parallel the cꢀaxis (Figure 2C). ACMꢀ1
shows permanent porosity upon activation at 75 ºC in
vacuo. Thermogravimetric analysis (TGA) shows that
loss of solvent from the pores occurs between 25–125 ºC
(~31% of the total starting mass), after which there is no
further mass loss until the onset of degradation ca. 325
ºC (Figure S2). The calculated BET surface areas using
CO2 and N2 are 1154 m2 g–1 and 1021 m2 g–1, respectiveꢀ
ly. The CO2 pore volume of 0.60 cm3 g─1 is in close
agreement with the value obtained using the VOID utiliꢀ
Scheme 1. Synthesis scheme for ACMꢀ1: (i) AsCl3, THF, –78
°C →25 °C; (ii) Pd(PPh3)4 (5 mol%), 4:1:1 toluene:ethanol:H2O,
105 °C, 96 h; (iii) Ni(BF4)2, 5:2:1 DMF:methanol:H2O, 75 °C,
48─96 h.
As a first demonstration of this principle, reaction of
TPPA and a secondary pillaring ligand (1,1'ꢀbiphenylꢀ4,
4'ꢀdicarboxylic acid; BPDH2) with Ni(BF4)2 at 75 °C in
an organic solvent mixture under N2 results in the forꢀ
mation of a single crystalline phase, named ACMꢀ1
(Scheme 1(iii)). ACMꢀ1 is cationic, having formula unit
[Ni2(ꢁ2ꢀOH)(TPPA)(BPD)][BF4], determined by single
crystal Xꢀray diffraction and confirmed by C,H,N,F elꢀ
emental analysis and FTꢀIR (Figure S1). The structure
of ACMꢀ1 was solved in the orthorhombic space group
Pnna (Z = 4). Each TPPA is coordinated to three symꢀ
metryꢀequivalent Ni(II) ions through its pꢀpyridylꢀN doꢀ
nors (Figure 1A); the phenylpyridine arms are twisted
into a propeller configuration commonly observed in
molecular systems. The inorganic nodes are comprised
Figure 2. Spaceꢀfilling representations of the extended structure
of ACMꢀ1 viewed in: (A) the crystallographic bcꢀplane; (B) in the
acꢀplane; (C) the abꢀplane, showing the cisꢀAs2 pockets (purple
atoms).
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ty in Platon (0.63 cm3 g─1; corresponding to a 53% acꢀ
cessible void space).16 ACMꢀ1 shows highly reversible
TypeꢀI sorption of a number of small molecule probe
gases without hysteresis (Figures 3A & S3). The measꢀ
ured adsorption capacities for various gases were: N2,
545 cm3 mmol─1 (77 K, 0.95 atm); CO2, 486 cm3 mmol─1
(196 K, 0.95 atm); O2, 575 cm3 mmol─1 (77 K, 0.20
atm); and H2, 218 cm3 mmol─1 (77 K, 0.95 atm).
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Closer examination of the extended structure of ACMꢀ
1 along the cꢀaxis reveals pairs of As atoms arranged in
a cisꢀorientation (Figure 2C & 4A; purple atoms). This
arrangement is derived from pairs of TPPA ligands
bridged faceꢀtoꢀface by coordination to [Ni2(ꢁ2ꢀOH)]3+
nodes (Figures 2C & 4A). Pairs of cisꢀAs atoms are
related by a 2ꢀfold inversion, so the lone pairs share a 2ꢀ
D plane, intersecting at a 98.8° apex (Figure S5). A geꢀ
ometric investigation of chelated molecular diarsine
complexes in the Cambridge Crystallographic Database
reveals As─M─As bite angles between 69.9–95.1º, which
are more acute than the puative 98.8º bite angle in ACMꢀ
1. Furthermore, hypothetical symmetric chelation of a
metal center into an As2 pocket in ACMꢀ1 would incur
M‒As distances of 3.18 Å (Figure S5); this is 31% longꢀ
er than the average M‒As bond found in the database
(2.43 Å; 2.21–2.91 Å; Figure S6). Thus, the cisꢀAs2
sites in ACMꢀ1 appeared to be too distal to readily cheꢀ
late lowꢀvalent metals.
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Figure 3. (A) Comparison of adsorption isotherms for ACMꢀ1
(solid markers) versus AuꢀACMꢀ1 (open markers): red = O2, 77
K; blue = N2, 77 K; green = CO2, 196 K; black = H2, 77 K.
(B) Comparison of the simulated and observed PXRD patterns
for ACMꢀ1 (black = model; blue = observed) and AuꢀACMꢀ1
(red = model; green = observed).
twisting of the As2 pocket, which moves adjacent As
lone pairs outꢀofꢀplane and facilitates coꢀcoordination of
two As─AuCl moieties per pocket (Figure 4A). The reꢀ
fined AuCl site occupancy from the SCXRD solution
was 78%, in excellent agreement with ICPꢀOES studies
(average AuCl loading = 78.1%; Table S1). AuꢀACMꢀ1
samples were also analyzed by a combination of PXRD,
scanning and transmission electron microscopy (S/TEM)
coupled with 2ꢀD energyꢀdispersive spectroscopy
(EDS), and Xꢀray photoelectron spectroscopy (XPS) to
confirm that no larger Au(0) species were present (Figꢀ
ures S8ꢀS11).
Accordingly, when freshlyꢀprepared ACMꢀ1 crystalꢀ
lites were treated with organic solutions containing
Group 10 precursors (e.g., K2PtCl4, Pd(COD)Cl2,
Pd(MeCN)2Cl2, Pt(SEt)2Cl2), no noticeable changes
were seen in the PXRD patterns. Alternatively,we treatꢀ
ed ACMꢀ1 with different Group 11 organometallic preꢀ
cursors, assuming that it might be possible to coꢀ
coordinate multiple metal centers into the same cisꢀAs2
pocket, to generate species that may not be observed in
solution. Direct treatment of ACMꢀ1 with (Me2S)AuCl
(4 eq. per TPPA) and standing overnight caused the crysꢀ
tallites to turn from emerald green to a darker grey color
and the bulk showed distinct changes to the PXRD patꢀ
tern (Figures 3B & S7B). Notably, the formation of
As─AuCl coordination bonds in ACMꢀ1 proceeded with
retention of crystallinity, permitting full SCXRD strucꢀ
tural resolution of the modified ACMꢀ1 using a convenꢀ
tional Xꢀray source.
Arguably, the most interesting aspect of this result is
the geometric nature of the Au dimers generated in Auꢀ
ACMꢀ1 (Figure 4A; inset): there is a very shortꢀrange
Au···Au contact distance of 2.76 Å in each dimer. Auꢀ
rophilic bonding between Au(I) centers is a wellꢀknown
phenomenon due to closedꢀshell 5d10 interactions, which
can enhance the solidꢀstate luminescence.17 Numerous
aurophilicallyꢀbonded complexes have been structurally
characterized; the shortest Au···Au distances are generalꢀ
ly correlated with the presence of more electronꢀ
donating ligands.18 Dimers with the general formula
[LAuX]2 (L = PR3, RCN, R=S, etc. ; X = Cl─, Br─, I─)
display Au···Au distances between 2.84─3.43 Å (avg. =
3.10 Å; Figure S12). It is therefore fascinating that an
extraordinarily short Au···Au distance is obtained using
ACMꢀ1 as an SSL, and that the [AsAuCl]2 dimers also
force a distortion of the MOF scaffold. Presumably, the
rigidity of the MOF limits the extent of this distortion,
resulting in significant compression of the Au···Au disꢀ
tance versus what is observed in geometricallyꢀrelaxed
The new material (AuꢀACMꢀ1) inhabits the same
space group as the parent MOF, with a noticeable distorꢀ
tion to the unit cell. The origin of this distortion is a
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Figure 4. (A) Comparison of single crystal structures of As2 pockets in ACMꢀ1 before and after addition of AuCl (Au = gold; Cl = dark
green). Inset: sawhorse projection of the aurophilicallyꢀbound Au2 dimers, with associated bond distances (Å). (B) Extended spaceꢀ
filling view in the acꢀplane showing location of AuCl moieties and retention of major pore openings.

Journal of the American Chemical Society
Page 4 of 6
*smh@cm.utexas.edu
Notes
(equilibrium) molecular complexes.
1
The solidꢀstate properties of AuꢀACMꢀ1 are also interꢀ
esting. First, the BET surface areas of AuꢀACMꢀ1
measured using both N2 and CO2 probe gases (664 and
674 m2 g─1, respectively; Figures 3A & S13) and the
corresponding pore volumes (0.28 and 0.34 cm3 g─1,
respectively) are between 40–50% lower than for the
parent ACMꢀ1; this is not unexpected due to the addition
of AuCl groups inside the micropores. However, the H2
capacity of AuꢀACMꢀ1 approximately doubles (218 to
454 cm3 mmol─1; Figure 3A). This is noteworthy since
the Auꢀfunctionalized material is significantly heavier
than ACMꢀ1 and indicates that H2 loading inside the
Au(I)ꢀdecorated pores is more optimal. Studies to better
understand this behavior, are currently under way using
inelastic neutron scattering spectroscopy (INS). Secondꢀ
ly, AuꢀACMꢀ1 shows enhanced solidꢀstate luminesꢀ
cence; materials containing aurophilic bonds are often
strongly emissive.17 Compared to the emission profiles
of ACMꢀ1 and the TPPA ligand, a distinct feature was
observed at 489 nm for AuꢀACMꢀ1 (in degassed CH2Cl2
at 77 K; Figure S14). The peaks observed at 431 nm and
463 nm are due to intraꢀligand transitions (n→π* and π
→π*), while the feature at 489 nm is likely also a ligꢀ
andꢀbased transition that is not observed for the free ligꢀ
and. The emission peaks for AuꢀACMꢀ1 were blueꢀ
shifteddue to lowering in energy of the ligand molecular
orbitals upon Au(I) binding; the sharpness and intensity
of the emission peaks of AuꢀACMꢀ1 were also inꢀ
creased, likely due to the heavyꢀatom effect.19 The exꢀ
cited state lifetimes for ACMꢀ1 (τ = 0.33 μs) and Auꢀ
ACMꢀ1 (τ = 0.49 μs) were longer than the lifetime of
free TPPA (τ = 0.28 μs), likely due to reduced conforꢀ
mational freedom of ligands in the MOF.In summary,
this initial work shows great promise for the use of orꢀ
ganoarsine MOFs decorated with coꢀoperative coordinaꢀ
tion pockets, as solidꢀstate ligands for the generation of
unusual, confined coordination complexes. We are presꢀ
ently investigating ways to tune the coordination pockets
in ACMꢀ1 to accommodate other lowꢀvalent metals of
interest for small molecule activations.
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors thank Drs. Vincent M. Lynch, Dwight Romaꢀ
novicz, and Hugo Celio for analytical assistance. This
work was supported by the NSF under grant number DMRꢀ
1506694 and the Welch Foundation (Fꢀ1738).
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on
the ACS Publications website. Full experimental proceꢀ
dures for TPPA, ACMꢀ1 and AuꢀACMꢀ1; characterizing
data for TPPA and the ACMꢀ1 materials; NMR, FTꢀIR,
TGA & XPS data; SEM/EDS and TEM images; additional
BET & PXRD data. CCDCꢀ1827947 and 1827948 contain
the CIF data for ACMꢀ1 and AuꢀACMꢀ1, respectively; this
12. (a) Mague, J. T.; Wilkinson, G. J. Chem. Soc. (A) 1966, 1736ꢀ
1740. (b) Cloyd Jr., J. C.; McAuliffe, C. A. Transition Metal
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grave, London, 1973.
13. (a) Kannan, S.; Kumar, K. N.; Ramesh, R. Polyhedron 2008, 27,
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information
is
available free of charge at:
www.ccdc.cam.ac.uk.
AUTHOR INFORMATION
Corresponding Author
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